Size Effect of Nanosheet on BN Fibers Derived from BNNS/Polyborazine Hybrid Precursor

doi:10.15541/jim20250275

Abstract

Abstract: BN ceramic fibers exhibit significant potential for applications in the high-temperature wave-transparent and semiconductor fields, due to their excellent resistance to high-temperature and thermal conductivity, as well as outstanding wave-transparent performance. However, the low crystallinity observed in BN ceramic fibers inhibits the complete realization of their superior properties associated with the h-BN crystal structure. In this work, based on the mechanism that inorganic nanofillers could act as heterogeneous nucleating agents to accelerate matrix crystallization, three lateral sizes of amino-functionalized BNNS were prepared utilizing a one-step ball milling method. BNNSs were chemical bonded to the molecular chain of polyborazine to synthesis hybrid BNNS/polyborazine precursors, which were finally derived to high performance BN ceramic fibers with high crystallinity. This investigation thoroughly explored the scale effect of BNNS on the molecular structure of hybrid precursor, as well as their physicochemical properties and melt spinning performance. The relationship among the BNNS size, microstructure, and mechanical properties was elucidated. Increasing BNNSs size could enhance the ceramic yield of precursor (up to 64.1%), but destroy the viscosity-time stability. Moreover, it was demonstrated that changing the BNNS scales could evidently regulate the crystal structure of BN ceramic fibers. Relationship among BNNSs lateral sizes, crystal structure, and mechanical performance was determined to be non-linear. BN ceramic fibers containing 2 μm BNNS displayed the highest crystallinity (94%), grain size (12.5 nm) and density (2.0 g/cm³). However, surface defects associated with 2 μm BNNS resulted in a non-optimal average strength (0.90 GPa). BN ceramic fibers doped with 0.5 μm BNNS exhibited the best average strength (0.94 GPa), attributed to the favorable combination of high crystallinity and a smooth surface. This work could provide crucial references for the fine regulation of microstructure and the preparation of high-performance BN ceramic fibers.

Key words: BN ceramic fiber, crystal structure, mechanical properties, BNNS, BNNS size effect

CLC Number:

TQ343

ZHANG Yunbo, WANG Bing, LI Wei, SONG Quzhi, DU Yiang, WANG Yingde. Size Effect of Nanosheet on BN Fibers Derived from BNNS/Polyborazine Hybrid Precursor[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250275.

References

[1] NACLERIO A E E, KIDAMBI P R R. A review of scalable hexagonal boron nitride (h-BN) synthesis for present and future applications.Advanced Materials, 2023, 35(6): 2207374.
[2] WANG B, CAI D, ZHU Q,et al. Mechanical properties and thermal shock resistance of SrAl₂Si₂O₈ reinforced bn ceramic composites. Journal of Inorganic Materials, 2024, 39(10): 1182.
[3] AN L, YU Y, CAI Q, et al. Hexagonal boron nitride nanosheets: Preparation, heat transport property and application as thermally conductive fillers. Progress in Materials Science, 2023, 138: 101154.
[4] LIN S, YE F, MA [J], et al. Fabrication and properties of porous boron nitride/silicon oxynitride ceramic composites via gas pressure sintering. Materials & Design, 2015, 87: 272.
[5] LIAO P, HE H, GUO H, et al. Highly thermally conductive boron nitride fiber. Acs Nano, 2025, 19(16): 16043.
[6] WANG Z, GE M, YU S, et al. Microstructures and properties of polymer-derived hexagonal boron nitride fibers with initial gradient oxygen contents. Materials Characterization, 2024, 207: 113503.
[7] ZOU C, GUO S, ZHOU X.Mechanical property and fracture behavior of borazine-derived bulk boron nitride ceramics reinforced with chopped Si₃N₄ fiber.Journal of Materials Engineering and Performance, 2025, 34(6): 4821.
[8] MIELE P, BERNARD S, CORNU D, et al. Recent developments in polymer-derived ceramic fibers (PDCFs): Preparation, properties and applications - A review. Soft Materials, 2007, 4(2-4): 249.
[9] DENG C, SONG Y, WANG Y, et al. Synthesis of polymeric precursor for boron nitride through substitution reaction of methylamine/dimethylamine. Acta Chimica Sinica, 2010, 68(12): 1217.
[10] HOSSAIN A, SOUVIGNET T, INNIS N R, et al. Two-step ALD process for non-oxide ceramic deposition: the example of boron nitride. Journal of Physics-Materials, 2024, 7(3): 035006.
[11] TOURY B, MIELE P, CORNU D, et al. Boron nitride fibers prepared from symmetric and asymmetric alkylaminoborazines. Advanced Functional Materials, 2002, 12(3): 228.
[12] LEI Y, WANG Y, SONG Y.Atmosphere influence in the pyrolysis of poly (alkylamino)borazine for the production of BN fibers.Ceramics International, 2013, 39(6): 6847.
[13] LI W, WANG J, XIE Z, et al. Synthesis and characterization of silicon-containing polyborazine to boron nitride ceramic fiber. Acta Chimica Sinica, 2011, 69(16): 1936.
[14] DU Y, WANG B, MENG F, et al. Nearly stoichiometric BN fiber with high crystallinity achieved by boron trichloride assisted curing process. Journal of the American Ceramic Society, 2022, 105(1): 82.
[15] LIU Y, PAN Y, YIN D, et al. Investigations on microstructure and mechanical properties of boron nitride fiber using experimental and numerical methods. Materials Today Communications, 2022, 33: 104554.
[16] BERNARD S, CHASSAGNEUX F, BERTHET M P, et al. Crystallinity, crystalline quality, and microstructural ordering in boron nitride fibers. Journal of the American Ceramic Society, 2005, 88(6): 1607.
[17] RAJABIFAR N, GHANEMI S, ROSTAMI A, et al. Synergistic impact of hybrid carbon nanotube and graphene on crystallinity and thermo-mechanical behavior of polymer blends. Polymer Composites, 2025, 46(2): 1416.
[18] SALEHI A, RAHMATI R, KHERADMANDKEYSOMI M, et al. Carbon nanotubes embedded in nanofibrillated epdm rubber as thermally and electronically conducting polypropylene nanocomposites for flexible electrostatic discharging. Acs Applied Nano Materials, 2025, 8(8): 3847.
[19] MANDAL S, ROY D, MUKHOPADHYAY K, et al. Mechanistic insight into the role of the aspect ratio of nanofillers in the gas barrier properties of polymer nanocomposite thin films. RSC Applied Interfaces, 2024, 1(5): 977.
[20] FENG L, GUO L, CHEN Q, et al. Tailoring the geometry of silicon nitride nanofillers to simultaneously strengthen and toughen carbon/carbon composites. Journal of Materials Science & Technology, 2024, 202: 183.
[21] ZHANG Y, WANG B, DU Y, et al. High crystallinity BN fiber derived from organic-inorganic hybrid BNNS/polyborazine precursor. Journal of the American Ceramic Society, 2025, 108(7): 20439.
[22] DU Y, WANG B, LI W, et al. Design and synthesis of a novel spinnable polyborazine precursor with high ceramic yield via one-pot copolymerization. Journal of the American Ceramic Society, 2021, 104(11): 5509.
[23] WANG G, SONG Y.Enhancing mechanical property of SiC fiber by decreasing fiber diameter through a modified melt-spinning process.Journal of Inorganic Materials, 2018, 33(7): 721.
[24] ZHANG Y, CHEN J, ZHANG H, et al. Hexagonal boron nitride ceramic reinforced with a dispersed glass phase and microdomain-extruded glass fibers. Journal of the European Ceramic Society, 2025, 45(10): 117362.
[25] MIELE P, TOURY B, CORNU D, et al. Borylborazines as new precursors for boron nitride fibers. Journal of Organometallic Chemistry, 2005, 690(11): 2809.
[26] MIELE P, TOURY B, CHASSAGNEUX F, et al. Correlation between structural features and mechanical properties of boron nitride fibers derived from alkylaminoborazines. Journal of the European Ceramic Society, 2005, 25(2): 157.
[27] WANG C, HONG C, YAN L,et al. Structural evaluation and mechanical property of boron nitride fibers during melt-drawn fabrication process. International Journal of Applied Ceramic Technology, 2018, 15(3): 660.
[28] VINCENT H, CHASSAGNEUX F, VINCENT C,et al. Microtexture and structure of boron nitride fibers by transmission electron microscopy, X-ray diffraction, photoelectron spectroscopy and Raman scattering. Materials Science and Engineering A-Structural Materials Properties Microstructure and Processing, 2003, 340(1-2): 181.
[29] WANG Z, GE M, YU S,et al. Microstructural evolution of polymer-derived hexagonal boron nitride fibers under high-temperature stretching. Journal of Advanced Ceramics, 2023, 12(10): 1973.
[30] GANESH R, OBAID A A, GILLESPIE J W.Experimental determination of bimodal strength distribution of S-glass fibers.Composites Part B-Engineering, 2023, 254: 110559.